KR830001192B1 - Continuous production method of olefin polymer or copolymer - Google Patents

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Description

Continuous production method of olefin polymer or copolymer

The present invention relates to a process for the continuous production of α-olefin polymers or copolymers. More specifically, the present invention is a liquid magnesium compound (A) which is soluble in a hydrocarbon solvent and does not contain an organoaluminum compound and a transition metal compound. The catalyst component (C) is introduced into the polymerization or copolymerization zone separately from the catalyst components (A) and (B) using a catalyst composed of a liquid transition metal compound (B) and an organoaluminum compound (C), or the catalyst component Part or all of (C) is added to the mixture of catalyst components (A) and (B) to polymerize or copolymerize the resulting mixture.

According to the method of the present invention, since the complicated reaction necessary for immersing the transition metal catalyst component in the prior art can be omitted, the excessive use of the transition metal is unnecessary and the generation of waste material can be prevented. . Therefore, according to the method of the present invention, the yield of polymer or copolymer is improved in addition to being advantageous in terms of cost and pollution control. Excellent effects such as narrow molecular weight distribution of the polymer or copolymer, narrow composition distribution, and excellent transparency of the copolymer can be obtained.

More specifically, the present invention is one or more electron donors (i) which are soluble in hydrocarbon solvents, do not contain organoaluminum compounds and transition metal compounds, and are selected from alcohols, organic carboxylic acids, aldehydes and amines. Polymerization or copolymerization in the presence of a catalyst composed of a liquid transition metal compound (B) and an organoaluminum compound (C) in a liquid phase magnesium compound (A) obtained by contacting with a halogen-containing magnesium compound (ii) (1). In addition, the compound (C) is injected into the polymerization or copolymerization zone separately from the other compounds (A) and (B), or part or all of the compound (C) is added to the other compounds (A) and (B). A transition metal characterized in that the polymerization is carried out while injecting the resulting mixture into the zone or adding a mixture of the compounds (A), (B) and (C) into the zone (2). A process for the continuous preparation or preparation of polymers or copolymers of alpha olefins characterized by continuous polymerization or copolymerization of up to 5 mole% of alpha olefins or alpha olefins with diolefins in a hydrocarbon solvent in the presence of a catalyst and an organoaluminum compound. To provide.

Conventionally, there have been various limitations on supporting a highly active transition metal catalyst component on several kinds of halogen-containing solid magnesium compounds. In other words, when the solid transition metal components obtained through a complex method are injected into the polymerization zone, the performance of the highly active solid transition metal catalyst components is various kinds of roasting components for the production of the solid transition metal compounds. Since it can be changed as predicted according to various blending methods for producing solid transition metal compounds and various blending components and methods, it is usually used as a solid transition metal catalyst component supported on a carrier. Came. Therefore, in the prior art, a complicated process was required to prepare a solid transition metal catalyst component, and the solid transition metal catalyst component was quantitatively injected into the polymerization zone to uniformly disperse the catalyst component in the polymerization zone. In order to solve this problem, special catalysts are required because the solid catalyst component is insoluble in the hydrocarbon solvent used for the polymerization. Also pay close attention to the above. Even if the solid-state transition metal catalyst component insoluble in a hydrocarbon solvent

In order to eliminate the above-mentioned adverse effects, it is necessary to use soluble magnesium compounds in the reaction solvent. Japanese Patent Publication No. 31968/71 (UK Patent Publication No. 1,235,062) and German Federal Patent Publication No. 1,924,709) and Japan National Patent Publication No. 39, l17 / 75 (British Patent Publication No. 1,358,437 and German Federal Republic Patent Publication No. 2,159,910).

However, when a soluble magnesium compound is used in the reaction solvent described in these patents, it is not possible to obtain a high yield comparable to the yield by a known technique that can be obtained using the above-described solid transition metal catalyst. The yields obtained by these patents are up to about 10 times higher than those without the magnesium compound.

Japanese Patent Publication No. 39, l17 / 75 mentioned above uses various magnesium compounds as a solution. For example, dissolution of magnesium diisopropylate and decanol with different molar amounts or use of cyclic magnesium in organic aluminum compounds as a solution is described in the above patent, but halogen-containing magnesium compounds such as cyclic magnesium are dissolved in alcohol. It is not described about making it. In addition, fulmarethylene obtained using the magnesium compound as described above in Examples 30 to 3 of the patent.

The present inventors have overcome the drawbacks of the low yield of the prior art using soluble magnesium compounds in the reaction solvent, and catalysts having the same or higher catalytic activity obtained by using a solid transition metal catalyst component insoluble in the reaction solvent. Various studies have been carried out to provide a method for preparing an alphaolefin polymer or copolymer which can be carried out in the above and also eliminates the above-mentioned drawbacks caused by the use of a solid transition metal catalyst component.

The inventors of the present invention have a novel technical way of thinking that is far from the prior art of dissolving halogen-containing magnesium compounds, namely the use of magnesium compounds soluble in the reaction solvent and the above-mentioned known organoaluminum compounds. Based on this, it has been found that improved methods of preparing alpha olefin polymers or copolymers can be achieved. More specifically, the present inventors obtained by dissolving a magnesium compound with a specific electron donor, soluble in a hydrocarbon solvent, and using an organoaluminum compound and a Changi metal compound.

The inventors also note that the molar ratio of electron donor (i) / halogen-containing magnesium compound (ii) is one or more. Preferably 2.3 or more. It has been found that the improved method can be particularly preferably achieved when particularly preferably 2.8 or more.

In addition, the present inventors can omit the process for preparing a solid transition metal catalyst component which requires complicated operation according to the improved method of the present invention, and does not need to pay close attention to injecting the solid phase component into the reaction zone. It can overcome the high cost and pollution effect caused by the use of a large amount of transition metal compound, can easily prepare olefin polymer or copolymer with a very low molecular weight distribution, and also have narrow composition distribution and transparency It has been found that good copolymers can be prepared.

It is an object of the present invention to provide a process for the continuous production of olefin polymers or copolymers which can achieve the abovementioned improvements and effects.

The above-described red eye and effects of the present invention will be described in detail below.

According to the method of the present invention, the continuous polymerization or copolymerization of alpha olefins is performed while injecting a liquid magnesium compound (A), a liquid transition metal compound (B) and an organoaluminum compound (C) into the polymerization or copolymerization zone. Compound (C) is formed by injecting into the zone separately from other compounds (A) and (B) or by adding some or all of compound (C) first to the liquid mixture of compounds (A) and (B) The mixture is injected into the reaction zone or the mixtures (A), (B) and (C) are mixed at the same time and injected into the polymerization zone.

The magnesium compound (A) which is soluble in polymerization and does not contain an organoaluminum compound and a transition metal compound is preferably an alcohol having 6 or more carbon atoms, preferably an organic carboxyl having 7 or more carbon atoms. Contacting a halogen-containing magnesium compound (ii) with at least one electron donor (i) selected from acids, preferably aldehydes having 7 or more carbon atoms and preferably alkylamines having 6 or more carbon atoms You can get

Examples of preferred magnesium compounds (ii) include magnesium halides such as magnesium chloride, magnesium embrittlement, magnesium iodide and magnesium fluoride, and magnesium chloride is preferred among them. Another magnesium halide. In particular, magnesium dichloride is preferable. And organic groups other than hydrocarbon groups, such as C ₂ -C ₁₀ alkoxy groups such as methoxy, ethoxy, protoxy, butoxy and octoxy groups, phenoxy, methylphenoxy, 2.6-dimethyl-phenoxy, naphthoxy C ₆ to C ₂₀ aryloxy groups such as seasons, fortmiloxy (HCOO-), acetoxy (CH ₃ COOO), propionyloxy (C ₂ H ₅ COO-), butyryloxy (C ₃ H ₇ COO- ), valeryl oxy (C ₄ H ₅ COO-), stearoyl weekends oxy (C ₁₇ H ₃₃ COO-), oleoyl-oxy (C ₁₇ H ₃₁ COO-), such as having a C _l ~C ₂₀ acyloxy group such as a Halogen-containing magnesium compounds can also be used. Halogen-containing magnesium compounds having an alkoxy group are preferred among the magnesium compounds except for magnesium halide, and these compounds can be prepared by reacting a Grimmer compound with an alcohol.

Moreover, magnesium compounds, such as alkoxymagnesium, aryloxymagnesium, acyloxymagnesium, or metal magnesium, can be used for halogenating agents, such as silicon tetrachloride, hydrogen chloride, and chlorine, or halogenated hydrocarbons, such as t-butyl chloride, allyl chloride, and diphenylmethyl chloride. Small groups can also be used as halogen-containing magnesium compounds produced by halogenation.

Of the halogen-containing magnesium compounds exemplified above, magnesium halides are most preferred.

The reaction conditions between the electron donor (i) and the magnesium compound (ii) depend on the type of the electron donor and the type of the halogen-containing magnesium compound and the type of the polymerization solvent. Both reactions are carried out in a hydrocarbon solvent using an excess molar amount of the electron donor. It is preferable to carry out by heating. In the magnesium compound (A), the molar ratio of the electron donor (i) to the halogen-containing magnesium compound (ii) is suitably one or more. However, when using magnesium dihalide as a halogen-containing magnesium compound, 2.3 or more are preferable.

For example, when alcohol is used as the electron donor, the amount of alcohol is preferably 1 mole or more, more preferably about 2.3 to about 20 moles, and particularly preferably about 2.8 to 10 moles, per 1 mole of the halogen-containing magnesium compound. . When magnesium halide is used as the halogen-containing magnesium compound, the amount of alcohol used is preferably 2.3 moles or more, more preferably about 2.5 moles to about 20 moles, more preferably about 2.8 to 10 moles, per mole of the halogen-containing magnesium compound. Moles are particularly preferred.

When aliphatic hydrocarbons and / or alicyclic hydrocarbons are used as the hydrocarbon solvent, alcohols having six or more carbon atoms with respect to one mole of the halogen-containing magnesium compound are preferably used as part of the alcohol. About 0.5 moles or more. Especially preferably, 0.7 mol or more should be used. At this time, alcohol having less than 5 carbon atoms can be used for the remaining alcohol. At this time, in the case of using magnesium dihalide as the halogen-containing magnesium compound, at least about 1.2 moles of alcohol having six magnesium phosphorus carbon atoms per mole of dihalide. Preferably at least about 1.5 moles are used.

By doing the above, the total amount of alcohol required for dissolving the halogen-containing magnesium can be kept low, and the resulting catalyst component has high activity.

In the case of using an aromatic hydrocarbon as the hydrocarbon solvent, the magnesium compound can be dissolved in the halogen group by using 1 mol or more of alcohol with respect to 1 mol of the halogen-containing magnesium compound, regardless of the type of alcohol.

The reaction of the electron donor (i) with the halogen-containing magnesium compound (ii) to produce the magnesium compound (A) is preferably carried out in a hydrocarbon solvent. Hydrocarbon solvents are the same aliphatic hydrocarbons as those exemplified for the synthetic solvent used in the method of the present invention. It can select from aromatic hydrocarbons and these halogen derivatives, and can use.

The reaction between the electron donor (i) and the halogen-containing magnesium compound (ii) is 0 ° C. or higher. It is preferably carried out at a temperature of at least 65 ° C, more preferably from about 80 to about 300 ° C, particularly preferably from about 100 to about 200 ° C. The reaction time may be appropriately selected, such as 1 minute or more, preferably about 15 minutes to about 5 hours, more preferably about 30 minutes to about 2 hours. A longer reaction time does not cause any drug effect.

The electron donor (i) is selected from alcohols, organic carboxylic acids, aldehydes and amines, alcohols having 6 or more carbon atoms, such as C ₆ -C ₂₀ alcohols, and C ₇ -C ₂₀ carboxylic acids. It is preferable to select among aldehydes having 7 or more carbon atoms, such as carboxylic acids C _{7 to} C ₁₈ aldehydes having 7 or more carbon atoms, and alkylamines having 6 or more carbon atoms, such as C ₆ C ₁₈ alkylamines. Do.

Specific examples of the alcohols of the electron donor (i) include 2-ethyl-butanol, n-octanol, n-octanol, 2-ethylethanol, decanol, dodecanol, tetradecyl alcohol and undeken, and oleyl alcohol. Aliphatic alcohols such as transfer and stearyl alcohol, alicyclic alcohols such as cyclohexanol and methylcyclohexanol, benzyl alcohol, methylbenzyl alcohol, isoprobenzyl alcohol, α-methylmaryl alcohol and α, α-dimethyl Aromatic alcohols such as benzyl alcohol, and aliphatic alcohols containing alkoxy groups such as n-butyl cellulose cooker and 1-butoxy-2-prothiol.

Examples of suitable carboxylic acids of the electron donor (i) include caprylic acid, 2-ethylhexanoic acid, undalesaric acid, nonyl acid and oncarbonic acid.

Examples of suitable aldehydes of the electron donor (i) include caprylaldehyde, 2-ethylhexyl aldehyde, capralaldehyde and undecylaldehyde.

Examples of suitable amines of the electron donor (i) include heptylamine, octylamine, nonylamine, decylamine, laurylamine, undecylamine, 2-ethylhexylamine and the like.

As the liquid transition metal compound (B) used in the method of the present invention, it is preferable to use titanium compounds or vanahep compounds, and among these, titanium compounds are preferable. For example, a tetravalent titanium compound represented by the general formula Ti (OR) _n X _4-n.

n

4이다.In the above formula, R represents a hydrocarbon group such as a roughened or unsaturated alkyl group which may be optionally substituted with a halogen atom, a lower alkoxy group, etc., X represents a halogen atom, and n is 0.

n

4

Specific examples of the titanium compound include TiCl ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₆ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₆ H ₅ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (OC ₄ H ₆ ) ₄ , T (OC ₉ H ₁₃ ) ₄ , Ti (OC ₆ H ₁₁ ) ₄ , Ti (OC ₈ H ₁₇ ) ₄ , Ti [OCH ₂ (C ₂ H ₅ ) CHC ₄ H ₉ ] ₄ , Ti (OC ₉ H ₁₉ ) ₄ , Ti [OC ₆ H ₃ (CH ₃ ) 2] ₄ , T ₂ (OCH ₃ ) ₂ (OC ₄ H ₉ ) ₂ , Ti (OC ₂ H ₄ Cl ) ₄ and _{Ti (OC 2 H 4 OCH 3} ) are _four and the like.

Examples of the titanium compound which can be used in addition to the above-described compounds are compounds having any crystal system and having low valences. Specific examples include 4-type TiC1 ₃ -A 4 salt TiC1 screen produced by reducing a titanium to aluminum metal -A ₃ type, produced by reducing TiCl 4 with hydrogen, a titanium salt screen ₃ is generated by reducing a titanium tetrachloride into titanium metal TiCl ₃ , Ti (Hydrogen) produced by reduction of titanium tetrachloride with organoaluminum compounds such as (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl and (C ₂ H ₅ ) 1.5AlCl _1.5 OCH ₃ ) ₃ , Ti (OC ₂ H ₅ ) ₃ , Ti (On-C ₄ H ₉ ) ₃ , Ti (OCH ₃ ) Cl ₂ , 2CH ₃ 0H and Ti (CH ₃ ) ₂ Cl · CH ₃ OH Alkoxytitanium (III) compounds and TiCl ₃ are produced by reduction with hydrogen or TiCl ₂ .

Solid transition metal compounds such as titanium trichloride and titanium dichloride are used in liquid form after the rough treatment operation. For example, this treatment process may be performed by converting an electron donor used to prepare a halogen-containing magnesium compound that is soluble in about 1 to 24 moles, preferably about 3 to 15 moles of hydrocarbon solvent per mole of the transition metal compound. It can be carried out by contact with. The treatment operation can be terminated only by partial dissolution of the transition metal compound. In this case, it is preferable to dissolve and use only the dissolved part of the transition metal compound.

The treatment operation may be performed at a temperature of about 65 ° C. or higher, preferably about 80 ° C. to about 300 ° C., particularly preferably about 100 ° C. to about 200 ° C., for at least about 15 minutes, preferably 20 minutes to 2 hours. There is a number.

If necessary, the solid transition metal compound can be dissolved in the liquid magnesium compound (A) obtained as described above and used as a liquid transition metal compound fire.

m

3이다. 바나듐 화합물의 특정한 예로서는 VOC1₃, VO(OC₂H₅)Cl₂, VO(OC₂H₅)_1.5Cl_1.5, VO(OC₄H9)₃, VO[OCH(CH₂)CHC₄H₉]₃및 VCl₄등이 있다.Vanadium compounds are, for example, compounds represented by the general formula VO (OR) _m X ₃ i _m or VX ₄ . In which R is as defined above and 0

m

3 Specific examples of vanadium compounds include VOC1 ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) _1.5 Cl _1.5 , VO (OC ₄ H9) ₃ , VO [OCH (CH ₂ ) CHC ₄ H ₉ ] ₃ And VCl ₄ and the like.

In the method of the present invention, as the organoaluminum compound (C), compound compounds containing at least one aluminum-carbon bond in the molecule can be used.

Examples of such organoaluminum compounds include compounds having the following general formula (I) and complex alkylation products of aluminum with a group 1 metal atom on the Mendelev periodic table having the following general formula (2).

R ¹ lAl (OR ² ) _s H _p S _q (1)

Wherein R ¹ and R ² are the same or different and usually represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and L, s, p and q are all 0 ≤ l, s, p, q <3. However, l + s + p + q = 3. Examples of R ₁ and R ₂ hydrocarbon groups are alkyl groups having 1 to 15 carbon atoms and alkenyl groups having 3 to 12 carbon atoms.

M ¹ AlR ¹ 4 (2)

In the above formula, M ¹ represents Li, Na, or K, and R ¹ is as defined above.

l

3범위내의 수가 바람직함). 일반식 R¹ℓAlX_3-ℓ의 화합물류(식중, R¹및 X는 상기에서 정의한 바와 같고, ℓ는 0<ℓ<3범위내의 수가 바람직함). 일반식 R¹ℓAlH₃ ^-ℓ의 화합물류(식중, R_l는 상기에서 정의한 바와 같고, ℓ는 2

ℓ<3범위내의 수가 바람직함) 및 일반식 R₁ℓAl(OR₂)_sX_q의 화합물류(식중, R₁및 R₂는 상기에서 정의한 바와 같고, )는 할로겐을 나타내며, 0<ℓ

3, 0

s<3, 0

q<3, ℓ+s+q=3임)등이 있다.As an example of the organoaluminum compound which has the said General formula (1), the compound of general formula R <^1> Al (OR <^2> ) _3- L (In general, R <^1> and R <^2> are as defined above and L is 1.5.

l

Number within the range of 3 is preferred). Compounds of the general formula R ¹ LAlX _3- L, wherein R ¹ and X are as defined above, and L is preferably a number in the range of 0 <L <3. Compounds of the general formula R ¹ LAlH ₃ ^- L (wherein, R _l is as defined above and L is 2

A number within the range of l <3 is preferred) and compounds of the general formula R ₁ lAl (OR ₂ ) _s X _q (wherein R ₁ and R ₂ are as defined above,) represent halogen, and 0 <ℓ

3, 0

s <3, 0

q <3, l + s + q = 3).

Specific examples of the organoaluminum compounds having the general formula (1) include trialkylaluminum such as triethylaluminum and tributylaluminum, trialkenylaluminum such as triisoprenylaluminum, and some alkoxylated alkylaluminum (such as diethyl Dialkylaluminum alkoxides such as aluminum oxide and dibutylaluminum butoxide), alkylaluminum sesquialoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, the average composition being R ¹ _2.5 Al ( OR ² ) a compound having _0.5 , some halogenated alkylaluminum (eg, dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum broide), ethylaluminum sesquichloride, butylaluminum sesquichloride and Alkyl aluminum sesquis such as ethyl aluminum sesquibrolide Alkylaluminum dihalides such as halides, ethylaluminum dicuroids, propylaluminum dibrolides and butylaluminum dibromide, some alkylaluminum hydrides (e.g. dialuminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride) Ride, ethylaluminum dihirai

In addition, organoaluminum compounds bonded by two or more aluminum atoms with an oxygen atom or a nitrogen atom can be used. As specific examples of these,

(C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ and (C ₂ H ₅ ) ₂ AlNAl (C ₂ H ₅ ) ₂ .

It is preferable to use a trialkylaluminum compound, an alkylaluminum halide, and a mixture thereof among the organoaluminum compounds (C) exemplified above.

According to the method of the present invention, a mixture of alpha olefins or alpha oles or a mixture of alpha olefins and diolefins of up to 5 mol% may be prepared using a liquid manganese compound (A), a liquid transition metal compound (B), and an organoaluminum compound ( C) is used for continuous polymerization or copolymerization in a hydrocarbon solvent. This polymerization is carried out by injecting compound (C) into the polymerization zone or the copolymerization zone separately from the other compounds (A) and (B), or a part or all of the compound (C) in liquid phase mixture with the other compounds (A) and (B). The mixture produced by addition to the polymerization zone or copolymerization zone

Examples of the alpha-olefin is a C ₂ ~C _20, preferably a C ₂ ~C ₁₂ alpha-olefins such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene and 1-octene.

Copolymerization is random copolymerization or block copolymerization. In copolymerization, diolefin, such as conjugated or nonconjugated diene, can be used in a maximum amount of 5 mol% as a comonomer. Examples of the diolefins are butadiene, isoprene, 1.4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 1.7-octadiene and the like. The diolefin may copolymerize in an amount of 0.1 to 5 mol%, preferably about 0.2 to about 3 mol%, in which case the iodine has about 5 to about 30, and a sulfur atom and a vulcanizable copolymer are obtained. The vulcanizates of the porous polymers have excellent properties

The polymer or copolymer obtained by the method of the present invention can be made of plastic or rubber.

Continuous polymerization or copolymerization by the process of the invention is carried out in a hydrocarbon solvent. Examples of these solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosine, their halogen derivatives, aromatic hydrocarbons such as benzene, matouene and xylene, and those such as chlorobenzene. Halogen derivatives. The olefins used for polymerization can also be used as a solvent.

In the polymerization zone or the copolymerization zone, the concentration of the transition metal compound in the hydrocarbon solvent is 0.0005 to about 1 drimol / liter, particularly about 0.001 to about 0.5 drimol / liter, in terms of the transition metal, and transition to the halogen-containing magnesium compound. The molar ratio of the metal compound is 0.005 to about 0.5, preferably about 0.01 to about 0.33, more preferably about 0.03 to about 0.25, and the molar ratio of the organoaluminum compound to the transition metal compound is about 5 to about 2,000, preferably about Under continuous polymerization or copolymerization under conditions of 20 to about 500

The concentration of the halogen-containing magnesium chemical is preferably about 0.001 to about 200 rim moles, and more preferably about 0,003 internal mass about 50 rim moles per 1 meter of liquid in terms of magnesium atoms.

In the method of the present invention, a continuous synthesis method is employed, which employs hydrocarbons containing polymers or copolymers produced by continuous injection of a mixture of alpha or olefins or a mixture of alpha and diolefins into a polymerization zone. Take out from the polymerization zone. Usually, it is preferable to continuously inject each of the catalyst components (A), (B) and (C), and these components can be injected at short intervals. In this case, components (A), (B) and ( C) is injected separately into the polymerization or copolymerization zone. Alternatively, a liquid mixture (hydrocarbon solution) of components (A) and (B) is prepared first, and then the mixture and component (C) are separately injected into the polymerization or copolymerization zone. Or part or all of component (C) is added to the aforementioned liquid mixture of components (A) and (B) to inject the resulting mixture and residual component (C) into the polymerization or copolymerization zone. In addition, compound (A). A mixture produced by mixing some or all of the compound (B) and the compound (C) may be injected into the polymerization zone. However, first, a method of mixing the compound (A) and (B) is preferable.

According to this method, it is assumed that the solid is precipitated in the polymerization or copolymerization zone. However, because the precipitates are extremely fine, dispersibility in the polymerization or copolymerization band is extremely good.

It is preferable to dissolve a component composed of an electron donor such as magnesium halide and an alcohol in the hydrocarbon solvent by the above-mentioned method and then inject it into the polymerization zone. When the above-mentioned dissolved component temporarily becomes solid by cooling or other operation, it can be re-dissolved by heating or other operation before use. However, when the total system temperature is higher than the melting temperature, the above heating operation is not necessary.

The polymerization or copolymerization temperature can be changed suitably such as the temperature is about 20 to 350 ° C, preferably about 65 to 300 ° C. In order to obtain an olefin copolymer having good transparency, it is preferable to use liquid phase polymerization in an inert hydrocarbon medium and to select a dissolution temperature of the resulting olefin copolymer. For example, when preparing a dendritic copolymer with ethylene and a small amount of other alpha olefins, the polymerization temperature is preferably in the range of the copolymer melting point to about 200 ° C. The polymerization pressure is from atmospheric pressure to about 100 kg /

In carrying out the process of the invention, organometallic compounds containing hydrogen, metal atoms of Group 2 of the periodic table and / or several electron donors, such as alcohols, ethers, amines, ketones, carboxylic acids, etc., in the polymerization zone , Amides, phosphorus compounds and sulfur compounds can be contained to control molecular weight and stereoregularity.

According to the present invention, a total residence with a low molecular weight distribution can be obtained. When adapting the method of this invention to copolymerization of 2 or more types of olefins, the copolymer of narrow composition distribution and favorable transparency can be obtained.

However, the method of the present invention is not limited to the above specific ones. For example, the polymer of a large molecular weight distribution can be obtained by using a molecular weight modifier using the method of the present invention, or the yield of an olefin polymer can be improved by combining two or more different polymerization conditions.

The present invention will be described in more detail by enumerating the following embodiments.

Example 1

A commercially available anhydrous magnesium chloride (50 g) was suspended in 1 liter of stagnant kerosene in a nitrogen stream, and 205 g of 2-ethylhexyl alcohol (1 mol of magnesium chloride 3 mol) was added thereto, followed by gradually heating while stirring the resulting mixture. After 1 hour of reaction, the solids disappeared completely and a colorless transparent solution was obtained. When the solution was cooled to room temperature, no solid precipitate was formed, leaving only a colorless and transparent solution. In this way, a magnesium chloride / 2-ethylhexyl alcohol complex was obtained as a solution in kerosene. Ti (On-C ₄ H ₉ ) ₄ 65.6 was added to this solution and the mixture was stirred well. A mixture solution of magnesium chloride / 2-ethylhexyl alcohol complex and Ti (On-C ₄ H ₉ ) ₄ was obtained. lost. The molar ratio of magnesium / titanium in the solution was 8.

100 liters of hexane dehydrated in a 200 liter molten continuous polymerization reactor, 36 drimol / hour of diethylaluminum monochloride, magnesium chloride / 2-ethylhexyl alcohol complex and Ti (On-C ₄ H ₉ ) ₄ (titanium) Continuously charged 0.45 drimol / hour, and simultaneously injected 12.Okg / hour of ethylene, 12.0 liters of 4-ethyl-1-pentene and 60 liters / hour of hydrogen into the reactor so that these monomers were Continuous polymerization was carried out at 140 ° C. under kg / cm 2 for an average residence time of about 1 hour. The copolymer concentration in the hexane solvent was 80 g / liter, and the polymerization activity of the catalyst was 17,800 g of titanium 1 mmol molar copolymer. The resulting copolymer had a density of 0.924 g / cm 3, a melt index of 2.66, and contained 14.4 of 1000 carbon atoms of isobutyl groups.

A 54 micron-thick film was prepared as this copolymer using a commercial tubular film forming machine (manufactured by Hyundai Machinery Co., Ltd.). The haze of the film was 9.4%, and molding conditions were as follows.

Resin Temperature: 170 ℃

Screw rotation speed: 60 times / min

Mold diameter: 100mm

Mold Slit Butterfly: 1.Omm

Comparative Example 1

Commercially available anhydrous magnesium chloride (50 g) was suspended in 2 liters of acid, and 3 mol of ethyl alcohol was added dropwise at room temperature over about 1 hour while stirring. After completion of the addition, the mixture was stirred for 30 minutes and hexane was removed in vacuo. The residue was dried and 700 mL of TiCl ₄ was added to the resulting mixture at 120 ° C. for 1 hour. The reaction mixture was filtered to give a titanium-containing solid phase catalyst. This catalyst contained 6.0 wt% titanium and 61.2 wt% chlorine atoms in terms of atoms.

Magnesium chloride / 2-ethylhexyl alcohol complex was injected without using a mixture solution of Ti (Ou-C ₄ H ₉ ) ₄ , and the titanium-containing solid catalyst obtained above was converted to titanium atoms in a continuous 0.45 mmol / hour injection. The copolymerization of ethylene and 4-ethyl-1-pentene was carried out in the same manner as in Example 1 except that the reaction was carried out. The concentration of the copolymer in the nucleic acid solvent was 53 g / liter, and the polymerization activity of the catalyst was 10,600 g of titanium 1 mmol molar copolymer. The density of the resulting copolymer was 0.922 g / cm 3. The cement ins was 4.1 and contained 14.4 carbon atoms of 1000 carbon atoms.

A film having a thickness of 54 microphones having a haze of 40.5% was produced from the copolymer using the same molding machine under the same molding conditions as in Example 1.

Comparative Example 2

Magnesium chloride / 2-ethylhexyl alcohol with no complex and a mixture of Ti (On-C ₄ H ₉ ) n and Ti (On-C ₄ H ₉ )

The operation of 1 was repeated except that an acid solution was used. Almost no polymerization proceeded and no measurement of properties was possible.

Example 2

In the same reverse-speed polymerization reactor as used in Example 1, nucleic acid was separately injected as a solvent, 100 liters / hour, 30 mmol / hour diethylaluminum monochloride, and the solution of magnesium chloride / 2-ethyl ethanol equivalent complex were converted into titanium atoms. A 2.4 mmol / hour, Ti (O _n -C ₄ H ₉ ) 4 hexane solution was continuously injected with 0.3 mmol / hour in terms of titanium atoms. Ethylene was continuously injected into the reactor so that the capacity in the reactor reached 30 kg / cm 2, and polymerization was performed at 140 ° C. with an average seizure time of about 1 hour. Hydrogen consecutive weeks

The polymer concentration in the solvent was 95 g / liter, and the polymerization activity of the catalyst was 31,700 g of 1 millimolar polyethylene of tyran. The density of the polymer was 0.966 g / cm 3 and the melt index was 7.0.

Example 3

A commercially available anhydrous magnesium chloride (50 g) was suspended in 1 liter of stagnant kerosene in a nitrogen stream, and 205 g of 2-ethylhexyl alcohol (1 mol of magnesium chloride 3 mol) was added thereto. The mixture was slowly heated while stirring and reacted at 130 ° C. for 1 hour. The solids were completely gone and a colorless and diseased solution was obtained. When the solution was cooled to room temperature, no solid precipitated door was formed, leaving only a colorless and transparent solution.

To this solution were added 13.Og of commercially available titanium chloride (trade name TAc-131, manufactured by Toho Titanium Co, Ltd., and 51.1 g of 2-ethyl equivalent alcohol).

The mixture was heated to 110 ° C. to obtain a green group solution. (Commercial magnesium chloride and titanium trichloride contain metal magnesium and metal aluminum as impurities, respectively, and these metals may be precipitated, but these precipitates do not affect the following polymerization reaction).

A mixture solution of magnesium chloride / 2-ethylhexyl alcohol complex and titanium trichloride was obtained as described above. This solution was clear at room temperature and the magnesium / tyran molar ratio in the solution was 8.

15 millimoles per hour of triethylaluminum, 15 millimoles per hour of diethylaluminum monochloride, and a mixture solution of the magnesium chloride / 2-ethylhexyl alcohol complex and titanium trichloride obtained as catalyst components were converted into titanium atoms to 0.5 millimoles per hour. Ethylene was continuously polymerized in the same manner as in Example 2 except for continuous injection into the polymerization reactor.

The polymer concentration in the solvent was 110 g / liter and the polymerization activity of the catalyst was 22 ² 000 g of polyethylene per millimolar of titanium. The polymer had a density of 0.968 g / cm 3 and a melt index of 2.3.

Comparative Example 3

10 g of commercially available titanium trichloride (TAC-131) was added in 1 L of kerosene, and 40 g of 2-ethylhexyl alcohol (6 mol of titanium trichloride) was added to the resulting mixture. The resulting mixture was heated at 100 ° C. Obtained.

Except for using a mixture solution of magnesium chloride / 2-ethylhexyl alcohol and titanium trichloride, and producing a titanium trichloride alcohol solution in terms of titanium atoms, except that 0.5 mmol / hour was continuously injected. Ethylene was reacted in the same manner as described above. Polyethylene could not be obtained at all.

Comparative Example 4

Commercially available Mgcl 2 (30 g) was suspended in 1 L of purified kerosene, and 43.5 g (3 mol of Mgcl ₂ mol 1 Mg) was added dropwise at room temperature. A portion of the resulting mixture was separated and warmed to avoid dissolution in kerosene. However, it became a viscous liquid during temperature increase and did not dissolve into kerosene. Thus, the slurry mixture obtained by adding ethanol was used for the following experiment.

To the Mgcl ₂ .3C 3 kerosene solution of a titanium chloride / 2-ethylhexyl alcohol complex obtained in 3 in ₂ H ₅ OH slurry in terms of the magnesium atom in 5 mmol / hour, and Comparative Examples obtained as described above as a catalyst component in terms of titanium atom Ethylene was continuously polymerized in the same manner as in Example 3 except that 0.5 mmol / hour was continuously injected.

The polymer concentration in the solvent was less than 5 g / liter and the catalyst activity was evenly low.

Example 4

100 liters / hour dehydrated hexane in the same 200 liter continuous polymerization reactor as used in Example 1. 40 mmol / hr of diethylaluminum 1 chloride, 10.8 mmol / hr of isoamyl ether, and 0.5 mmol / hr of a mixture solution of the magnesium chloride / 2-ethylhexyl alcohol obtained in Example 2 and titanium trichloride were converted into titanium atoms. Continuous injection and at the same time ethylene 12kg hours, 1-butch 12.4 to 13 liters / hour and hydrogen 30 to 50 liters / hour is continuously injected to average residence time at a polymerization temperature of 130 ℃ under voltage 24 to 27 kg / ㎠ For 1 hour

The resulting polymer had a density of 0.890 g / cm 3, a melt index of 3.92 and an ethylene content of 91.5%. In this copolymer, the content of the soluble portion of boiling methyl acetate was 0.6%, and the copolymer hardly became viscous.

The haze of the 1-mm-thick thin plate which produced this copolymer by the conventional method was 18%.

Comparative Example 5

Commercially available magnesium chloride anhydrous (20 g) in a stainless steel (SUS-32) ball mill cylinder containing 100 stainless steel (SUS-32) balls with an internal capacity of 800 ml, an internal diameter of 100 mm and a diameter of 15 mm. And 4 g of Tibl 3 (TA-131) were charged under a nitrogen stream, and then spun at 125 rpm for 120 hours. The powdered product was taken out from the mill and placed in a nitrogen filling container. The amount of titanium supported was 40 mg with respect to 1 g of the solid. In this way, a solid titanium catalyst was obtained.

Continuation of ethylene and 1-butene in the same manner as in Example 4, except that magnesium chloride / 2-ethylhexyl alcohol was used as the solid titanium catalyst obtained above instead of a mixture solution of cold water and titanium trichloride. The polymerization was carried out. A copolymer of ethylene and 1-butene was obtained in an amount of 2.8 kg / hour, and the polymerization activity of the catalyst was 5,600 g of copolymer per millimolar of titanium.

The density of the resulting copolymer was 0.892 g / cm 3, melt index 2.17 and ethylene content 84.1 mol%. In this copolymer, the content of the soluble portion of boiling methyl acetate was 1.5%, and the copolymer was polarized and tacky.

The haze of the 1-mm-thick thin plate which produced this copolymer by the conventional method was 58%.

Example 5

Into a 3-liter reactor equipped with a reflux condenser, 58.3 g (2.4 mol) of metallic magnesium and 1 liter of hexane were injected, followed by 2.4 mol of ethyl silicate (Kanto Chemical Co., Ltd.) and kerosene iodine solution (iodine was dissolved in kerosene). 6 ml) was added. The mixture was heated to 70 ° C. and nC ₄ H ₉ Cl was added dropwise over 1 hour. After the addition was completed, the mixture was reacted at 70 ° C. for 4 hours, and then filtered to obtain a solid reaction product MG (OC ⁵ H ₂ ) Cl.

50 g of the resulting Mg (OC ₂ H ₅ ) Cl was suspended in 1.5 liter of kerosene and 186.5 g of 2-ethylhexyl alcohol (3 mol per mol of M (OC ₂ H ₅ ) Cl) were added. The mixture was heated to 130 ° C. while stirring to react for 1 hour. The solid Mg (OC ₂ H ₅ ) Cl disappeared completely and a clear solution was obtained, leaving only a clear solution at room temperature.

Ticl ₃ (TAC-131) was added to the resulting solution of Mg (OC ₂ H ₅ ) Cl / 2-ethylhexyl alcohol complex so that the Mg / Ti molar ratio was 10. The solid TiCl ₃ was heated to 100 ° C. Disappeared and a clear yellowish-black solution of the Mg (OC ₂ H ₅ ) Cl / 2-ethylhexyl alcohol complex and TiCl ₃ mixture was obtained, leaving only a clear solution at room temperature.

40 mmol / h of diethylaluminum monochloride as a catalyst component, a solution of the mixture of Mg (OC ₂ H ₅ ) Cl / 2-ethylhexyl alcohol complex and Ticl ₃ obtained above, in terms of tyran atoms were continuously injected for 0.5 mmol / h. Except for the above, continuous polymerization of ethylene was performed in the same manner as in Example 2.

Polyethylene was obtained in an amount of 6.8 kg / hour, and the polymerization activity of the catalyst was 13,600 g of polyethylene per mol of titanium. The density of the polymer was 0.961 g / cm 3 and the melt index was 0.50.

Example 6

0.4 liters / hour of dehydrated keroseyl solvent in an atmospheric pressure continuous polymerization tank (overflow type) having an average volume of 2 liters, triisobutylaluminum 0.7 chloride / hour, 2.3 mmol / hour diethylaluminum 1 chloride, 2- 1.28 mmol / h ethylhexyl alcohol, a solution of the mixture of magnesium chloride / 2-ethyltylsilyl alcohol complex obtained in Example 1, and Ti (On-C ₄ H ₉ ) ₄ were continuously injected with 0.03 mmol / h in terms of titanium atoms. (The catalyst component was injected with an amount converted into kerosine so that the amount of kerosine solvent injected was 0.6 liter / hour). At the same time, a gaseous mixture of ethylene and propylene (ethylene / propylene molar ratio 40/60) was passed through the polymerization tank at a rate of 200 liters / hour, and copolymerization was carried out at a temperature of 90 ° C. During the continuous polymerization the polymer solution was a homogeneous clear solution and no gel formed.

Precipitated copolymer was precipitated from excess methanol to give ethylene / propylene copolymer at a rate of 328 / hour. The polymerization activity of the catalyst was 1.070 g of copolymer per millimolar of titanium. The melt index of the copolymer was 1.92 and the ethylene content was 75.1%. In this high polymer, the content of the soluble portion of boiling methyl acetate was 0.7%, and the copolymer hardly became viscous.

The haze of the thin plate of 1 mm thickness which produced this copolymer by the conventional method was 12%.

Comparative Example 6

The same method as in Example 6, except that the titanium-containing solid phase catalyst obtained in Comparative Example 1 was used instead of the mixed solution of magnesium / 2-ethylhexyl alcohol complex and Ti (O _n -C ₄ H ₄ ). As a result, copolymerization of ethylene and propylene was performed continuously. This polymer mixture was in the form of a slurry with suspended particles (which can be thought of as crystals) and was white in appearance and turbid.

The copolymer of ethylene and propylene was obtained in an amount of 29 g / hour, and the polymerization activity of the catalyst was 970 g of copolymer per mol of titanium. The melt index of the copolymer was 6.84 and the ethylene content was 68 mol%. The content of the soluble portion of boiling methyl acetate in the copolymer was 2.0%, and the copolymer was extremely tacky.

The haze of the 1-mm-thick thin plate which produced this copolymer by the conventional method was 58%.

Example 7

10 g of TiCl ₄ was suspended in 100 mL of purified kerosene and 4.5 mL of Al (C ₂ H ₅ ) _1.5 Cl _1.5 was added dropwise at 0 ° C. over 30 minutes with stirring. The mixture was heated to 80 ° C. over 30 minutes and reacted for 1 hour. The reaction mixture was cooled to room temperature and the supernatant was decanted to obtain solid titanium trichloride.

The titanium trichloride obtained above was added to the kerosene solution of the magnesium chloride / 2-ethylhexyl alcohol complex obtained by the method similar to Example 1 so that Mg / Ti molar ratio might reach 10. The mixture was heated to 100 ° C. to freeze a cyan clear solution, leaving only a clear solution at room temperature. Thus, a mixture aqueous solution of magnesium chloride / 2-ethylhexyl alcohol complex and titanium trichloride was obtained.

Ethylene and ethylene were prepared in the same manner as in Example 6 except for using the titanium-containing mixed solution obtained above instead of the mixture solution of magnesium chloride / 2-ethylhexyl alcohol complex and Ti (O _n -C ₄ H ₉ ) ₄ . Propylene was copolymerized. A copolymer of ethylene and propylene was obtained in an amount of 27 g / hour, and the polymerization activity of the catalyst was 900 g of copolymer per millimolar of titanium. The melt index of the copolymer was 2.27 and the ethylene content was 81.2 mol%. The content of soluble sites of boiling methyl acetate in the copolymer was 0.6% and the copolymer hardly became viscous.

The haze of the 1-mm-thick thin plate which produced this copolymer by the conventional method was 15%.

[Examples 8 to 13]

The procedure of Example 2 was repeated except that the type of titanium compound, the molar ratio of magnesium / titanium and the type of organoaluminum compound were changed as described in Table 2, and the results are also described in Table 1.

[Table 1]

Example 14

Commercially available MgCl ₂ (30 g) was suspended in 1 L of kerosene, and 192.6 g of 2-ethylbutyl alcohol (6 mol per mole of magnesium chloride) was added to the mixture, followed by heating with stirring. MgCl ₂ was dissolved at 140 ° C. resulting in a colorless transparent solution. The solution was cooled to become white at about 60 ° C., resulting in a solid precipitate, but became a clear solution above about 60 ° C. The mixture produced by adding commercially available titanium trichloride (TAC-131) to the solution was heated to 100 ° C so that the molar ratio of Mg / Tl reached 10.

Example 3 except that 30 mmol / hr of triethylaluminum as a catalyst component, 30 mmol / hr of diethylaluminum monochloride and the titanium-containing solution obtained above were continuously polymerized into 0.5 mmol / hr in a polymerization reactor to convert into titanium atoms. Ethylene was polymerized in the same manner as in. The catalyst for the titanium component injection, the pipe, and the pump was maintained at 100 ° C to prevent precipitation of solids.

The concentration of the resulting polymer in the solvent was 98 g / liter, the polymerization activity was 19,600 g of polyethylene per millimolar of titanium, and the melt index of the polymer was 4.8.

Example 15

A titanium-containing solution was prepared by adding TiCl ₄ to the magnesium chloride / 2-ethylbutyl alcohol complex in the same manner as in Example 14 in an amount of up to 12 Mg / Ti molar ratio. Ethylene was continuously polymerized in the same manner as in Example 14 using a titanium-containing mixed solution. The concentration of the resulting polymer was 77 g / liter, the polymerization activity of the catalyst was 15,400 g of polyethylene per millimolar of titanium, and the melt index of the polymer was 2.6.

Example 16

Suspended commercially available magnesium chloride (50 g) was suspended in 1 L of kerosene under nitrogen flow, and 136.5 g of 2-ethylhexyl alcohol (2 mol per mol of magnesium chloride) was added to the resulting mixture, followed by heating while stirring at 130 DEG C for 1 hour. I was. Only the solid phase remained. The mixture was cooled to room temperature, and a solid phase precipitated out. The supernatant was taken out and analyzed, and it was found that magnesium chloride was dissolved.

The same polymerization as in Example 2 was carried out except that the resultant dissolved magnesium chloride and a titanium trichloride / alcohol solution obtained in the same manner as in Comparative Example 3 were used.

The concentration of product polymer in the solvent was 67 g / liter. The polymerization activity of the catalyst was 22,000 g of polyethylene per millimolar of titanium, and the melt index of the polymer was 3.9.

Example 17

Suspended commercial nitrogen magnesium chloride (50 g) was suspended in 1 liter of purified kerosene under nitrogen flow, and 136.3 g of 2-ethylhexyl alcohol (2 mol per mol of magnesium chloride) and 24 g of ethanol (equivalent to magnesium chloride) were mixed. The mixture was slowly heated while stirring water and reacted at 120 ° C. for 1 hour. The solids disappeared completely, leaving a colorless clear solution. After cooling the solution, the solution became white at about 40 ° C and became white, but only a clear solution remained above about 40 ° C.

Ti (O _n -C ₄ H ₉ ) ₄ was added to the resulting magnesium / 2-ethylhexyl alcohol / ethanol complex in an amount of up to 10 Kg / Ti molar ratio.

The polymerization of ethylene was carried out in the same manner as in Example 14 except that the resulting titanium-containing mixed solution was used.

The concentration of the resulting polymer in the solvent was 90 g / liter, the polymerization activity of the catalyst was 18,000 g of polyethylene per millimolar of titanium, and the melt index was 5.8.

Example 18

Commercially available MgCl ₂ (50 g) was suspended in 2.5 liters of kerosene, and 586.5 g of lauryl alcohol (6 mol per mol of Mgcl ₂ ) was added to the resulting mixture, followed by heating while stirring to give a clear solution at 140 ° C. When the solution was cooled, a solid precipitated out at about 40 ° C., but a clear solution remained above about 40 ° C.

A commercially available Ticl3 (TAC-131) was added to the resulting Mgcl ₂ -lauryl alcohol complex solution in an amount of up to 10, and the solution was heated to 100 DEG C to produce a bluish green transparent solution. When the solid matter precipitated below about 40 ° C., it was separated into a bluish green solution and a white solid, and a clear solution remained above about 40 ° C.

Except for using the produced titanium-containing mixed solution, ethylene was subjected to continuous polymerization of ethylene in the same manner as in Example 14.

The polymer concentration in the solvent was 85 g / liter, the polymerization activity of the catalyst was 17,000 g of polyethylene per millimolar of titanium, and the melt index of the polymer was 6.3.

Example 19

A commercial product Mgcl ₂ (50 g) was suspended in 500 ml of ketosine, and 292.5 g of laurylamine (3 mol per mol of Mgcl ₂ ) was added to the resulting mixture, and the resulting mixture was slowly heated while stirring to give a clear solution at 110 ° C. or higher. . After cooling the solution, a solid precipitate was formed at about 75 ° C. The solution was reheated to 75 ° C. or higher to give a clear solution. In this way, an Mgcl ₂ -laurylamine complex solution was obtained.

To the resultant Mgcl ₂ -laurylamine complex solution, commercially available trichloride cyclic titanium (TAC-131) was added in an amount of up to 10 molar ratio of Mg / Ti, followed by 6 moles of laurylamine based _on 1 mole of Ticl _3. The resulting mixture was heated to 100 ° C. to obtain a bluish-green uniform transparent solution. Ethylene polymerization was carried out in the same manner as in Example 14 except that a vivid titanium oil solution was used.

The concentration of the resulting polymer in the solvent was 58 g / liter, the polymerization activity of the catalyst was 11,600 g of polyethylene per millimolar of titanium, and the melt index of the copolymer was 1.3.

Example 20

A commercial product MgCl ₂ (50 g) was suspended in 500 ml of ketosine, and 387 g of undesyleic acid (4 mol per mol of MgCl ₂ ) was added to the resulting mixture. The resulting mixture was gradually heated to give a clear solution at 95 ° C. or higher. This solution became a clear solution under room temperature.

As in Example 2, except that 40 mmol / h of diethylaluminum monochloride, 5 mmol / h of the resulting magnesium solution, and 0.5 mmol / h of Ti (On-C ₄ H ₄ ) 4 were continuously injected as catalyst components. Continuous polymerization of ethylene was performed by the method.

The concentration of the product polymer in the solvent was 48 g / liter, the polymerization activity of the catalyst was 9,600 g of polyethylene per millimolar of titanium, and the melt index of the polymer was 0.85.

Example 21

Under a nitrogen stream, commercially available magnesium anhydrous magnesium (50 g) and 134.4 g of 2-ethylhexyl aldehyde (6 mol per mol of magnesium chloride) were added to 500 mL of kerosene, and the resulting mixture was heated with stirring to react at 130 DEG C for 1.5 hours. The reaction mixture turned into an almost colorless transparent solution. The solution was left at room temperature to precipitate a small amount of white solid.

24 mmol / h of diethylaluminum monochloride, 0.4 mmol / h of Ti (On-C ₄ H ₉ ) ₄ and the supernatant of the reaction product obtained above were injected separately into the reactor with 2.4 mmol / h into the reactor. The polymerization of ethylene was carried out in the same manner as in Example 2 except for the one described above.

The concentration of the resulting polymer in the solvent was 59 g / liter, the polymerization activity of the catalyst was 14,800 g of polyethylene per millimolar of titanium, and the melt index of the polymer was 1.0.

Example 22

Suspended commercially available magnesium chloride (40 g) was suspended in 1 L of purified ketocin under nitrogen stream, and 150 g (3 mol per mol of magnesium chloride) of n-butyl cellussolve was added to the mixture to stand. When it reached C, 150 g of n-butyl cellussolve was further added, and the reaction was carried out at 90 DEG C for 1 hour to yield a pale yellow transparent solution, which remained a clear solution even at room temperature.

100 mmol / h of diethylaluminum monochloride, 0.5 mmol / h of Ti (On-C ₄ H ₉ ) _4, and 5 mg / h of the resulting magnesium solution in terms of magnesium atoms were continuously injected into the polymerization reactor as catalyst components. Then, continuous polymerization of ethylene was performed in the same manner as in Example 2.

The concentration of the resulting polymer in the solvent was 42 g / liter, the polymerization activity of the catalyst was 8,400 g of polyethylene per millimolar of titanium, and the melt index of the polymer was 1.8.

Example 23

Suspended commercial anhydrous magnesium chloride (21 g) in 500 ml of toluene under nitrogen stream, 40 g of n-propyl alcohol (3 mol per mol of magnesium chloride) were added, and the resulting mixture was slowly heated while stirring to react at 80 DEG C for 1 hour. The result was a colorless clear solution which remained clear even at room temperature.

Ti (On-C ₄ H ₉ ) ₄ was added to the resulting MgCl ₂ / n-propyl alcohol solution in an amount of up to 8 molar ratio of Mg / Ti.

Polymerization of ethylene and propylene was carried out in the same manner as in Example 6 except that toluene was used as the polymerization solvent and the diluent for the catalyst line segment, and the titanium-containing solution obtained above was used.

A copolymer of ethylene and propylene was obtained in an amount of 25 g / hour, and the polymerization activity of the catalyst was 830 g of a titanium milliliter molar copolymer. The melt index of the copolymer was 1.86 and the ethylene content was 78 mol%. The soluble site content of boiling methyl acetate in the copolymer was 0.7%, and the copolymer hardly became viscous.

The thin plate haze of 1 mm thickness which produced this copolymer by the conventional method was 20%.

Example 24

_{Ti (On-C 4 H 9} ) , except instead of _four to the _{Ti (On-C 4 H 9} ) 4 Cl 2 hexane solution with titanium atom in terms of the lost a 0.24 mmol / hr, and by the same method as in Example 2 Ethylene was polymerized. The polymerization activity of the catalyst was 38,000 g of polyethylene per millimolar of T, the melt index of the resulting polyethylene was 6.9 and the density was 0.966 g / cm 3.

Example 25

Suspended commercial anhydrous magnesium chloride (50 g) in 1 L of purified kerosene under nitrogen stream, and oleyl alcohol (2.5 mol per mole of magnesium chloride) was added to gradually increase the temperature while stirring the resulting mixture at 130 ° C for 1 hour. The reaction was carried out for a while to completely remove the solids and give a yellow clear solution. The solution was cooled to room temperature and 8.9 g of commercially available Ti (On-C ₄ H ₉ ) ₄ was added thereto, but the precipitate was not precipitated as any solid and the solution became a uniform transparent solution. In this way Magnesium Chloride / Eurail

The polymerization half-loss used in Example 1 was adjusted so that the supply line for the catalyst component coincided with the site almost identical to the solvent supply line. One line of these line layers was fed triethylamine and diethylaluminum monochloride, respectively, at a rate of 10.8 mmol hours, and the other line was a mixture of magnesium chloride / oleyl alcohol complex and Ti (On-C ₄ H ₉ ) ₄ . The solution was fed at a rate of 0.27 mmol / hr in terms of titanium atoms. Cycletohexane was continuously injected into the solvent feed line at a rate of 80 liters / hour. The concentration of titanium was 0.009 mmol / hr and the concentration of aluminum was 0.74 mmol / hr when the catalyst components were mixed. The time required for the mixture to reach the polymerization reactor from the mixing of the catalyst components was about 30 seconds, and the temperature was fixed at 140 ° C. Ethylene was injected into the polymerization reactor at a rate of 12.Okg / hour and continuously synthesized at a temperature of 200 ° C. and a voltage of 40 kg / cm 2, and the molecular weight of polyethylene was adjusted by continuously injecting hydrogen gas.

The polymer concentration in the solvent was 78.1 g / liter, and the polymerization activity of the catalyst was 23,100 g / cm 3 of polyethylene per millimolar of titanium. The density of polyethylene was 0.966 g / cm 3 and the melt index was 7.9.

Example 26

As in the ethylene polymerization of Example 3, diethyl, which is a component of the aluminum catalyst component, is not separately injected into the polymerization reactor with an organoaluminum compound, a magnesium chloride / 2-ethylhexyl alcohol complex, and a mixture solution of titanium trichloride. The catalyst component rate was injected so that the aluminum monochloride was matched with one solvent supply line (the concentration of titanium and aluminum was maintained at 0.01 mmol / liter and 0.6 mmol / hr, the temperature was 140 ° C., and The time required for the mixture to reach the polymerization reactor was 15 seconds). Further, triarytyl aluminum was continuously continued in the polymerization reactor. Except for the foregoing, ethylene was continuously polymerized in the same manner as in Example 3.

The polymer concentration was 120 g / liter and the polymerization activity was 24,000 g polyethylene per millimolar of titanium. The melt index of the resulting polymer was 2.4 and the density was 0.967 g / cm 3.

Example 27

Synthesis of Mg (OC ₂ H ₅ ) Cl in the same manner as in Example 5 and then suspended 50 g of Mg (OC ₂ H ₅ ) Cl in 1.5 liter of kerosene and 192.1 g of oleyl alcohol (Mg (OC ₂ H) ₅ ) The resulting mixture was added at a temperature of 50 ° C. for 30 minutes to remove the solid phase Mg (OC ₂ H ₅ ) Cl, and a clear solution was obtained. Also remained a clear solution.

Ti (OC ₈ H ₁₇ ) ₄ was added to the Mg (OC ₂ H ₅ ) Cl / oleyl alcohol complex solution in an amount of up to 10 molar ratio of Mg / Ti, resulting in a transparent homogeneous solution. This gave a solution of Mg (OC ₂ H ₅ ) Cl / tol alcohol and Ti (OC ₈ H ₁₇ ) ₄ mixture.

40 mmol / h of diethylaluminum monochloride as a catalyst component, a solution of a mixture of Mg (OC ₂ H ₅ ) Cl / tolyl alcohol complex and Ti (OC ₈ H ₁₇ ) _{4 in} terms of titanium atom, was continuously injected with 0.5 mmol / h. Except for the above, continuous polymerization of ethylene was performed.

Polyethylene was obtained at a rate of 0.7 kg / hour and the polymerization activity was 14,000 g of polyethylene per millimolar of titanium. The melt index of the polymer was 0.75 and the density was 0.963 g / cm 3.

Claims (1)

Soluble in a hydrocarbon solvent, free from organoaluminum compounds and transition metal compounds, and obtained from contact with at least one electron donor selected from alcohols, organic carboxylic acids, aldehydes and amines with a halogen-containing magnesium compound. Polymerization or copolymerization is carried out in the presence of a catalyst composed of a magnesium compound (A), a liquid transition metal compound (B), and an organoaluminum compound (C); While injecting the compound (C) into the copolymerization zone to be polymerized separately from the other compounds (A) and (B), part or all of the compound (C) is a liquid phase of the other compounds (A) and (B) Carrying out polymerization or copolymerization while injecting the resulting mixture into the zone or adding a mixture of compounds (A), (B) and (C) to the zone; A polymer or air of an alpha olefin characterized by continuous polymerization or polymerization of an alpha olefin or an alpha olefin and up to 5 mole% of a hydrocarbon solvent in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound. Process for the continuous preparation of coalescing.